Improving fastness to crocking of azoic dyed materials using certain vinyl resins



Patented Nov. 13, 1951 VINYLRESINS AZOIC DYED MATERIAIZS'USIN G ElmeFR Rossin; Meli'ose, Mass assi gnorjo 4 'santo Chemical GompanwSt. Louis, Mo., a corporation of Delaware N Drawing: Aiiplioatieh Mai-285 1948;

Serial No.-29;923

The present invention relates to-a method of improving the fastness to crocking, or rub-oil? of azoic dyed or naphthol dyed cotton textile and other similarly 'dyed 'ellulosi'c materials; I v

Azoic' dyes or naphtholcolors; which terms are usedinterchangeably hereinafter, generally have exeelleht wash-'fastness ar'iddighfifastriess and are generally considered'to be on a'par withvat dyes thisrespect. In addition, az oic dye'shave an" economidadvant'a'ge over vat dyes when either iii-aybe usedifo'ra particular dyeing job. How= ever; azoiedyed'fabrics have'on'e disadvantage which has not been satisfactorily overcome in the past, namely, the 'crocking' 01*rubbin'g' off of the dye from the surface" of the dyed fabric. Anil n berof techniques have been developed 'whioh tend to lessen the degree of crockingb'f suolidyes, but none have been successful heretofore; and forth'is andother reasons the widespread use of azoic yes has beenvmaterially. curtailed.

The. present invention. rovides a simple'and efiicient. method for overcoming-1. the 1 aforemen tioned difiiculties and permit the widespread use of azoi'c eyes for dyeing: an types of cell'fil'o'sic fabric'sand dther cellulosi l'naltii'ali and also other materials which may be dyed'with azoio dyes. The present invention" a 's'aeroviasfan azoic "dyed cellulosio Ifiaterial which is "substa tially fast tocrockingvri after" a considerable number'of Iaunderings';

'It is, accordingly, one object of sthe present inv'ehtionto provide a method of iriipi'vlng'wth fastness to cro'cking of azoicdye'd c'llulo's'ic' tei'- tiles and other 061111165 materials;

A further Object of the iliv'ntiol i'is t6 piov'id an azoie dyedcotton' or other cellulosicmaterial Which is substantially fast to Cibkifig and which retains its fastiiess" to crocliin'g'aftr alnurnbr of cotton washes or laundrings;

Other objects and advantages of the invention will. appear ffo'rii the following,desfifitionsand the appendedcl-aiins.

These and other objects are, in gnerallQQalttained by first impregnating the cotton teitil'e such as a fabri oriy'ai'n or other cellulosic-material, with a naphthol developing agent such :as p-n-aphthol, certain derivatives of B-hyd-ro'xy naphthoic acid and the like and then" coupling the developer in situ on the-cotton textileor other cellulosic material with -adiazot-ized wbase or salt iioiaims. (0 :24:18;

2 a Bene fs'faltiilv @0105 index eiipr i hle' stf f a 1: un rm-Y a eeqicdied metme n iibeeqiw textile or other cellulosio naterial is then impregnated with ansaqueous solution on prisifig a rela i yd d n acid? 9 l y ha ies 9 1 we m ht t lc rqq emeifis mm 1 to cet onx 9 3 .19 m xt h ee semi hen ridnr f r b1 -at-e Ya ,ie pei iurse t 1 11 2 1 the e rib ymer eltt .de ire venunTh e ne-m tmd-p se es ev a d en: tages over-prior m ethods of dyeing with azoic y s. infii e ne 2199 16:j ll ii weii ia me I th d ied f tt t developer h s e n pl ss t i li .d t 9?" 15;? necessary"to soap an nse such niaterialafter eeme i s V been co iipl ed ifi situ." 7 However; either looth fiithss e z 'st ii fi' x mews e zia ii e 1 6. de i e v ii eflqe e iq 9 the r i1 te. he manner indicated is-of particular imp ance 'si-nee it is well lgnown thata c llul ler shade isobi talliedwhen the rnaterial iS dried after the tie-'- veloper has beefiappnea; ,e t

tie-ammon um 'or afi iiieisalts-or' aniidated derivatives of; foregoingio "b yii'iefs whi o h may e S employed inthe practice of the man: ti'on include the salts of ammoniaor an amine as; fonexaifiple, -,fneth'y1 ethyl", pr'a'pyi; buty'l aniine -v 'w 7h l,.,, V r dated'deriva lves'of s h opol'yiners' will beak} saie'mts hose skil are Ofthe salts an derivativesaforementioned, thafii'mbmum saltis preferred; 7

The'fastnessto erokineof"theazoidyedinate rial; prepared as "des'ciibed shave-is, in-geniefalj made substantially permanent by heating the f'aIoiiC *orzrhateiiarto a tfifiifatfiie ofabeilt 230 ET-to 325 FE; a -teniperaturexof =about230 to 260 Fi being preferred-5 However a good perniane'nt effect may be obtained by h'eating 'the "treated fabric at'teniperaturesofi180 to 230" F1" In the latternase' 'good fastness to croc'king' will still be" apparent aftefa number: of "laundefin'gs orco'tton washes: Excellent: fastne'ssvtoficrecking; whicl-i ene polyamines such as ethylene diamines, propylene diamines, butylene diamines, diethylene triamine and the like may be used. The quantities of such thermosetting resin formaldehyde or'polyamine which can be used may be varied to some extent, but, in general, such materials are-employed in quantities varying between about 5 to by weight based on said copolymeric salt.

The copolymers which are employed in the present invention may be prepared in various ways. In general, they are prepared by copolymerizing an ethylene fi-dicarboxylic acid or anhydride such as maleic acid, fumaric acid,

maleic anhydride and the like, or preformed alkyl half esters of such acids in which the alkyl groups contain from 1 to 6 carbon atoms or mixtures of such acids, anhydrides or'esters, with a polymerizable vinyl compound having the structural formula R,CH='CH2, where R is a phenyl radical, a halogen substituted phenyl radical such as chloro-phenyl dichloro-phenyl and the like or a methyl substituted phenyl radical such as methyl phenyl, dimethyl phenyl and the like or mixtures thereof. In general, the above described dicarboxylic components and vinyl compounds are copolymerized in a molal ratio varying between about 1:1 to 1:2, and preferably in a molal ratio varying between about 1:1.1 to 121.5. Of the above described copolymerizable components, styrene and maleic anhydride, or styrene and mixtures of maleic anhydride and alkyl half esters of maleic acid, in which the alkyl group contains from 1 to 4 carbon atoms, are preferably employed in the preparation of such copolymer.

When alkyl half esters of ethylene a,B-dicarboxylic acids or anhydrides are employed as indicated, they are in general prepared by reacting an appropriate alcohol having from 1 to 6,and preferably 1 to 4, carbon atoms, such as methanol, ethanol and the like with such acid or anhydride in a molal ratio varying between about 1:1 to 1 :2. A variety of copolymerization methods may be used depending upon the mutual solubility or non-solubility of the above described polymerizable components. In the case of styrene and maleic anhydride, for example, the well-known mass polymerization may be used since these monomers are mutually soluble. In this method the monomers are copolymerized by heating them at temperatures varying between about 100 to 300 F. for a period of several hours, if desired, in the presence of a polymerization catalyst such as a peroxide catalyst, for example, benzoyl peroxide.

Emulsionpolymerization methods may be used or the monomers may be copolymerized in a nonreactive solvent such as xylene, which is a solvent for certain of the above monomers, butis a non-solvent for the copolymer. The temperature of the reactants is generally maintained at the boiling point of the solvent. The copolymer, which precipitates as it is formed, is separated from the liquid phase by centrifuging, filtration and the like.

The amnonia or amine salt of the copolymer is prepared, for example, by adding the copolymer to an aqueous solution containing a quantity of ammonia, amine and the like sufiicient to yield a solution of the copolymer in water. The solution obtained is not necessarily a true solution and in most instances will probably be a colloidal solution.

A further understanding of the invention will be obtained from the following illustrative examples, parts being by weight.

Example I A wax-free, clean cotton fabric was padded through a long bath (10 parts liquid to 1 part .fabric) comprising a naphthol developer. This bath Was made up as follows:

' 7 Parts Naphthol AS (p-hydroxy naphthoic acid anilide) 10 Ethanol 12 Water 10 NaOH (as an aqueous solution containing 330 parts NaOH/950 parts water) Formaldehyde (37%) 30 The above NaOH solution was added until the solution turned clear brown. The above ingredients were then added to 1000 parts of water to which had been added 2 parts of a 30% solution of. sodium dodecyl benzene sulfonate in water and 13.5 parts of 38 B. NaOH solution. The bath was maintained at about 70-80 C. during the padding operation and the pick-up was such as to put on a quantity of liquid substantially equal to the dry fabric weight. I The fabric comprising the developer was then padded through a long bath (10-1) comprising a diazotized salt which coupled with the developer in situ on the fabric. This bath had the following composition:

This solution was maintained at about 60 F. after preparation and during the padding operation. '1 he pad rolls were adj Listed so as to obtain about pick-up.

The dyed fabric was then padded through a solution containing two parts of the ammonium salt of the copolymer prepared as described below per 98 parts of water. This solution was maintained at about F. during the padding operation and the pad rolls were adjusted so as to obtain a 100% pick-up of the solution.

After the fabric had been treated by the above procedure, it was dried at a temperature of 250 F. The finished fabric which possessed a bright red'shade, had a slightly stiffened hand and excellent fastness to crocking. The fabric was boiled in a solution containing 2% sodium dodecyl benzene sulfonate for one hour without any appreciable red coloration of the solution and on drying was substantially fast to crocking. The fabric was then given three standard AATCC cotton washes and its fastness to crocking was not appreciably affected thereby.

' The ammonium salt of the copolymer employed' as described above was prepared by first reacting 0.2 molecular proportions of methanol with l molecular proportion of maleic anhydride at a temperature of about 75 C. until the reactiom product had I: a substantially constant acid valua ion-l continued heating "I'helresultingmixture was. then copolymerized with-about 1.04 -molecular proportions of styrene byheatingthe 'nlassto a. temperatureot about=80 -Ceand main taining this temperature during the period: :of

rapid heatevolution, after whichthe tempera and 132 par-ts.of:26--B; ammonia. solution. This solution was. then. diluted with i808'0a. pants: of

-watertolfor-m ausolutioncontaining' approximate.- lyi2- parts oi-.:the ammonia .saltzdofi' thecopolymer pep 9.8-: parts of water (asemployed-uaboveh Escmplell Atskeinbf wax-fredclean 1.05s oottonyarnwas immersed in a. 1ong;;bath, (1,0. parts li uidzto. 1 part fabric). comprising .a1.naphthol develsmer.

flhis bath. was made unby first mixin 10, parts otrnaphthol As, 1-2 .parts .oflethanolgand lilparts of; water= andthen. adding an aqueoussodiummy, droxide solution (containine... 32. parts. NaQH needed parts of water.) .untiLthe-sclution turned clear; brown. 'Iihirty. parts .of 3.71%.- formaldehyde Werelthenadded toqthelaboye ingredients and the wholewasadded to IOOQpartsof water tolwhich hadwbeen added 2 parts. of' a, 30%solutionoi sodium. dodecyl. benzene sulfonate. in water; and 1:i5 .par.ts ch38? B.....Na0Hiso1ution. Theresulting bath was. maintained ateo C, ,durinathe impregnating operation. The. skein; was run through. a. wrineer. after immersion the, bath. Thelskein comprising the..developer-was then immersed for aboutZ- minutes. in a. long. bath 1.011 containinafim partstoflxscdiumi chloride 15,; parts. of-Fas1-,..Scarlet Salt..,RN; (color in: dex.-.118) pen 990 parts. of, waten. This :bathwas maintained ataboutfiO? aiter-prenaratiomand during the immersion of. the-skeintherein. cess bath. was, removed by runningihe; skein through a conventional wringing: device.

The-,skein ofv dyedlyarn was ,then. immersedzfor twomirmtesina solution-prepared by firstndis: solving.:200 parts of. the comminutedmesin or: 09? polymer, as prepared ;in .Example. .I; in 2500 parts of a water to which .had: been. added. 132 parts -..of 25; B.: ammonia.solutiomandithen dilutingihis solution. with 5070; parts .of water. containing; 25

. par-ts of formaldehyde. This .solutionwasmain- Examplelll 211$: packages or 12'scotton yarn wound on coiled= spring cores were treated 1 on a Franklin Package Machineusing long-bath (19-1) containing ;a developer; This bath was prepared as described "in Examples I V and II andtmaintained at, about 70C; duringthe package treatment:

The circulationof the bath through the-packages wasias follows (using 5 lbs; gauge-pressure) Minutes Inside of package toward outside, 5 Outside. of. package toward, inside 5 Inside o packa e rd o tside-gl i 10. Outside of package toward inside. 10

The packages were then treated witha. long; bath (10-1) containing 20 parts; of sodium chlo-. ride and 15 partsof Fast Scarlet Salt-.RN (color index 118) per 990 parts of water. Thisbath was maintained at about 65- F. duringthe treatment. The bath was circulated through. the packages; from inside to outside and outside toinside using. the same schedule as given above.

The packages were next treated with the-solution of the ammonium salt ofthe copolymer: prepared as described: in Example I (abouti'2. parts of the ammonium salt of the copolymer per-98 parts of water). This-solution was maintained at about 125. F. and. was, circulated through the packagesusing the same schedule as.-

waslusedwith the bath containing the developer;

The packages were hydro-extracted for 2 minutes,

to crocking and retained thisproperty after 3" Washes with boiling 3% soap solution, each wash being of lhour duration, This dyedyarn, when beamed, canbe wovendirectly into, a fabric with?" outany further treatment.

The foregoing conditions such as temperatures, strengths of solution of the developer, diazotized salt and copolymer, pressure and circulation employed in package treatment, durationof dyeing and treatment with the copolymericsalt, and. other conditions may be variedconsiderably in. carrying out the practice of the inventionas will, be. apparent to ,those skilled inthe art. Specifi: cally, however, it is preferred to employ an. aqueous solutionof thecopolymeric salt of j the. typehereinbefore. described in which such copoly meric salt is present in amounts rangingv from about 0.5' to 5.0% by weight. The, quantity. of,- copolymeric salt actually deposited ;on the fabric or yarn will vary. depending upon. the amount, for. example that. is. picked up by padding or. the extent. to which the-yarn or fabric is,,ex.-- tracted, wrung, centrifuged or the like. In genev eral, from 0.4 to 5.0%. by weight of the copolymericsalt is deposited on the fabric, yarnbr. the material which vhas been dyed, based on .the, Weight of, such material.

Cellulosicv materials other than cotton fabrics and yarns can also. .bedyed with azoic dyes and. rendered fast to crocking by the method described herein. Asexamples oisuch materials may be. mentioned fabrics, and yarns fabricated from jute, flax, linen, viscose rayon, cuprammonium rayon. and the like orfabrics made from a combination ofyarns. fabricated from such materials. Other cellulosic materials can also be treated "by the process or method described herein, if desired Instead of forming azoic dyes or naphthol colors insitu on" cellulosic materials" bythe procedure hereinbefore described; other techniones may be used'toapplysuchdyes insitu to fabrics or yarns. Moreover; other-combinations of-naphthol developer anddiazoti'zedsalt' or base may be used d'eepnding upon-theshade;

'Naphthol Developer Diazo salt or Base Naphthol AS (B-l)1ydroxy naph- Fast Garnet B Base (color ine thoic acid anilid dex 82).

fl-Naphtliol.

Naphthanil AS-D (B-hydroxy Do.

naphthoic acid o-toluide) Naphthanil BS (B-hydroxy naph- Do.

tlioic acid m-nitroanilide). Naplitlianil BS (fi-hydroxy naph- Do thoic acid a-naphthalide). Naphthanil MX (fl-hydroxy naph- Do thoic acid m-xyllde). Naphthanil L (B-hydroxy naph- Do thoic acid o-anisid Naphtbanil OP (fl-hydroxy naph- Do.

thoic acid o-phenetidc). Naghthanil RL (fl-hydroxy napli- Do.

t oic acid p-anisid Naphthanil SW (B-hydroxy naph- Do.

thoic acid fl-naphthilide). Any of the above developers Faist (grunge R Base (color inex Do Fast Scarlet G Base (color index 68). -Do Fast Scarlet R Base (color index 69). Naphthol AS diazotized m-nitro-p-toluidene. Anyof the above developers Feast BB Base (color infi-Naphthol Blue Red 0 Base (color index 123). G Base (color index 258). Fast Blue B Salt (color index 499). Azo Block 0 Base (color index 500).

In addition to the combinations described in the above table, other combinations may be used as will be apparent to those skilled in the art.

The color index referred to above is that published by the Society of Dyers and Colourists, edited by F. M. Rowe, 1st edition (1924). e

Other means or procedures of dyeing fabrics or yarns with azoic dyes may be used in addition to those which have been described. For example, fabrics may be dyed in various types of apparatus by applying the developer first followed by coupling in situ with the diazo salt or base, or the developer and diazo salt or base in stabilized form may be applied to the fabric simultaneously. Moreover, yarns may be dyed on a beam or dyed as a running thread or by other procedures. The above described copolymerie salts may also be applied to fabrics, cotton raw stock, yarn and the like by the use of various types of equipment and by various modes of application.

The process described herein may also be employed to render fabrics, which have been printed with azoic dyes, substantially fast to crocking. The fabric may be printed by applyin the developer and diazo salt or base, respectively, either successively 01' simultaneously. After the fabric has been printed with the azoic dye, it may be top printed with an aqueous solution of the copolymeric salt or such solution ma be applied to the printed fabric in other ways.

Still further modifications of the process described herein will be apparent to those killed in the art.

What is claimed is: I

1. A process of improving the fastness to crocking of azoic dyed cellulosic materials which comprises first forming an azoic dye in situ on a cellulosic textile material selected from the group consisting of natural and regenerated cellulose textile materials by treating said material with a naphthol developer and a coupling agent selected from the group consisting of diazo salts and bases, subsequently treating said material with ill anaqueous solution comprising from 0.5.,to 5% by weight of a water-soluble salt of a copolymer of 1 to 2 molecular proportions of a polymerizable vinyl compound having the structural formula RCH=CH2, where R is selected from the group consisting of the phenyl radical, a halogen substituted phenyl radical and a methyl substituted phenyl radical, with 1 molecular proportion of an ethylene a,fi-dicarboxylic compound selected from the group consisting of maleic anhydride, maleic acid, fumaric acid and alkyl half esters of said acids, in which the alkyl group contains from 1 to 6 carbon atoms, and mixtures of these compounds, said salt being selected :from the group consisting of ammonium and amine salts, said solution being supplied in an amount sumcient to provide from about 0.4 to.5% by weight of said salt based on the weight of the material; and drying said material at temperatures above about F. to substantially insolubilize said salt. 2. A process of improving the fastnss' to cracking of azoic dyed cellulosic materials which comprises first forming an azoic dye in situ on a cellulosic textile material selected from the group consisting of natural and regenerated cellulose textile materials by treating said material successively with a naphthol developer and a coupling agent selected from the group consisting of diazo salts and bases; subsequently treating said material with an aqueous solution comprising from 0.5 to 5% by weight of a water-soluble copolymer of 1 to 2 molecular proportions of styrene with 1 molecular proportion of an ethylene 0.,[3- dicarboxylic compound selected from the group consisting of maleic anhydride, maleic acid, fumaric acid and alkyl half esters of said acids, in which the alkyl group contains from 1 to 6 carbon atoms, and mixtures of these compounds, said salt being selected from the group consisting of ammonium and amine salts, said solution being supplied in an amount sufiicient to provide from about 0.4 to 5% by weight of said salt based on the weight of the material; and drying said material at temperatures above about 180 F.'for a period of time sufiicient to substantially insolubilize said salt. s

3. A process of improving the fastnessto crocking of azoic dyed cotton textile materials, fabric or yarn which comprises first forming an azoic dye in situ on a cotton textile material by treating same successively with a naphthol developer and a coupling agent selected from the group consisting of diazo salts and bases; subsequently treating said material with an aqueous solution comprising from about 0.5 to 5% by wei ht of a water soluble ammonium salt of a copolymer of 1 to 2 molecular proportions of styrene with 1 molecular proportion of a mixture of maleic anhydride and an alkyl half ester of maleic acid, in which the alkyl group contains from 1 to 4 carbon atoms, said solution being supplied in an amount sufiicient to providefrom about 0.4 to 5% by weight of said salt based on the weight of the material; and drying said material at temperatures above about 230 F. fora period of time sufficient to substantially insolubilize said ammonium salt. v

4. A process of improving the fastness to crocking of azoic dyed cotton textile materials which comprises first forming an azoic dye in situ on a cotton textile material-by treating same successively with a naphthol developer and a conpling agent selected from thegroup consisting of diazo salts and bases; subsequently treating said material with anaqueous solution'co'mprising from about 0.5 to 5% by weight of a watersoluble ammonium salt of a copolymer of 1 to 2 molecular proportions 'of styrene with 1 molecular proportion of a mixture of maleic anhydride and methyl acid maleate, said solution being supplied in an amount sufficient to provide from about 0.4 to 5% by weight of said salt based on the weight of the material; and drying said material at a temperature above about 230 F. for a period of time sufiicient to substantially insolubilize said ammonium salt.

5. A process substantially according to claim 4, wherein the ammonium salt is the ammonium salt of a copolymer of 1 to 2 molecular proportion of styrene with 1 molecular proportion of a mixture of maleic anhydride and ethyl acid maleate.

6. A process substantially according to claim 4, wherein the ammonium salt is the ammonium salt of a copolymer of 1 to 2 molecular proportions of styrene with 1 molecular proportion of a mixture of maleic anhydride and propyl acid maleate.

7. A process of improving the fastness to cracking of azoic dyed cotton textile materials which comprises first forming an azoic dye in situ on a cotton textile material by treating the material successively with a naphthol developer and a coupling agent selected from the group consisting of diazo salts and bases; subsequently treating said material with an aqueous solution comprising from about 0.5 to 5% by weight of a water-soluble salt of a copolymer of 1 to 2 molecular proportions of a polymerizable vinyl compound having the structural formula R-CH=CH2, where R is selected from the group consisting of the phenyl radical, a halogen substituted phenyl radical and a methyl substituted phenyl radical, with 1 molecular proportion of an ethylene afi-dicarboxylic compound selected from the group consisting of maleic-anhydride, maleic acid, fumaric acid and alkyl half esters of said acids, in which the alkyl group contains from 1 to 6 carbon atoms, and mixtures of these compounds, said salt being selected from the group consisting of ammonium salts and amine salts, and from about 5 to 20%, based on said salt, of a substance selected from the group consisting of thermosetting resins, formaldehyde and alkylene polyamines, said solution being supplied in an amount sufficient to provide from about 0.4 to 5% by weight of said salt based on the weight of the material and drying said material at a temperature between about 230 and 325 F. for a period of time suffioient to insolubilize said salt.

8. A process substantially according to claim 7 wherein said substance is a urea-formaldehyde thermosetting resin.

9. A process substantially according to claim 7 wherein said substance is formaldehyde.

10. A process substantially accordin to claim 7 wherein said substance is diethylene triamine.

11. An azoic dyed cellulosic textile material characterized by fastness to crocking, prepared by treating a cellulosic textile material selected from the group consisting of natural and regenerated cellulose textile materials with a naphthol developer and a coupling agent selected from the group consisting of diazo salts and bases, subsequently treating said material with an aqueous 7 solution comprising from 0.5 to 5% by weight of a water-soluble salt of a copolymer of 1 to 2 molecular proportions of a polymerizable vinyl compound having the structural formula RCH=CH2 where R is selected from the group consisting of the phenyl radical, a halogen substituted phenyl radical and a methyl substituted phenyl radical, with 1 molecular proportion of an ethylene a,p-dicarboxylic compound selected from the group consisting of maleic anhydride, maleic acid, fumaric acid and alkyl half esters of said acids, in which the alkyl group contains from 1 to 6 carbon atoms, and mixtures of these compounds, said salt being selected from the group consisting of ammonium salts and amine salts, said solution being supplied in an amount sufficient to provide from about 0.4 to 5% by weight of said salt based on the weight of the material; and drying said material at temperatures above about 180 F. to substantially insolubilize said salt.

12. An azoic dyed cellulosic textile material characterized by fastness to crocking, prepared by successively treating a cellulosic textile material selected from the group consistin of natural and regenerated cellulos textile materials with a naphthol developer and a coupling agent selected from the group consisting of diazo salts and bases, subsequently treating said material with an aqueous solution comprising (1) from 0.5 to 5% by weight of a water-soluble salt of a copolymer of 1 to 2 molecular proportions of a polymerizable vinyl compound having the structural formula RCH=Cl-I2, where R is selected from the group consisting of the phenyl radical, a halogen substituted phenyl radical and a methyl substituted phenyl radical, with 1 molecular proportion of an ethylene a, 3-dicarboxylic compound selected from the group consisting of maleic anhydride, maleic acid, fumaric acid and alkyl half esters of said acids, in which the alkyl group contains from 1 to 6 carbon atoms, and mixtures of these compounds, said salt being selected from the group consisting of ammonium and amine salts and (2) a substance selected from the group consisting of thermosetting resins, formaldehyde and alkylene polyamines, said solution being supplied in an amount sufficient to provide from about 0.4 to 5% by weight of said salt based on the weight of the material; and drying said material at temperatures above about 180 F'. to insolubilize said salt.

ELMER H. ROSSIN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,047,398 Voss July 14, 1936 2,322,333 Widmer June 22, 1943 2,356,879 Pense Aug. 29, 1944 2,416,884 Schreiber Mar. 4, 1947 OTHER REFERENCES Silk Hour. and Rayon World for October 1947, pp. 46, 48, 51. 8-18.

Am. Dyestufi Reporter for April 22, 1946, p.- P197. 8-55.

Ser. No. 397,138, Fikentscher (A. P. C.), pub- Q lished May 11, 1943, 

1. A PROCESS OF IMPROVING THE FASTNESS TO CROCKING OF AZOIC DYED CELLULOSIC MATERIALS WHICH COMPRISES FIRST FORMING AN AZOIC DYE IN SITU ON A CELLULOSIC TEXTILE MATERIAL SELECTED FROM THE GROUP CONSISTING OF NATURAL AND REGENERATED CELLULOSE TEXTILE MATERIALS BY TREATING SAID MATERIAL WITH A NAPHTHOL DEVELOPER AND A COUPLING AGENT SELECTED FROM THE GROUP CONSISTING OF DIAZO SALTS AND BASES, SUBSEQUENTLY TREATING SAID MATERIAL WITH AN AQUEOUS SOLUTION COMPRISING FROM 0.5 TO 5% BY WEIGHT OF A WATER-SOLUBLE SALT OF A COPOLYMER OF 1 TO 2 MOLECULAR PROPORTIONS OF A POLYMERIZABLE VINYL COMPOUND HAVING THE STRUCTURAL FORMULA R-CH=CH2, WHERE R IS SELECTED FROM THE GROUP CONSISTING OF THE PHENYL RADICAL, A HALOGEN SUBSTITUTED PHENYL RADICAL AND A METHYL SUBSTITUTED PHENYL RADICAL, WITH 1 MOLECULAR PROPORTION OF AN ETHYLENE A,B-DICARBOXYLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF MALEIC ANHYDRIDE, MALEIC ACID, FUMARIC ACID AND ALKYL HALF ESTERS OF SAID ACIDS, IN WHICH THE ALKYL GROUP CONTAINS FROM 1 TO 6 CARBON ATOMS, AND MIXTURES OF THESE COMPOUNDS, SAID SALT BEING SELECTED FROM THE GROUP CONSISTING OF AMMONIUM AND AMINE SALTS, SAID SOLUTION BEING SUPPLIED IN AN AMOUNT SUFFICIENT TO PROVIDE FROM ABOUT 0.4 TO 5% BY WEIGHT OF SAID SALT BASED ON THE WEIGHT OF THE MATERIAL; AND DRYING SAID MATERIAL AT TEMPERATURES ABOVE ABOUT 180* F. TO SUBSTANTIALLY INSOLUBILIZE SAID SALT. 